Gilsonitic product and its manufacture



UNITED STATES.

CHARLES 1v. ronnns'r, or

mwn, HAROLD 'PATE NT OFFICE.

SHIP, MIDDLESEX COUNTY, NEW JERSEY, AND ORIN It. DOUT HETT, OF BEAVERFALLS, PENNSYLVANIA, ASSIGNOBS TO THE PHILADELPHIA, PENNSYLVAN ACORPORATION OF WEST VIRGINIA.

GILSONITIC PRODUCT AND ITS MANUFACTURE.

.No Drawing.

Z '0 all whom it, may concern:

Be it known that we, CHARLES N. FORREST, of Rahway, in the county ofUnion and State of New Jersey, HAROLD P. HAYDEN, of Raritan Township, inthe county of Middlesex and State of New Jersey, and ORIN R;DoUTrrE'r'r, of Beaver Falls, in the county of Beaver and State ofPennsylvania, citizens of the United'States, have invented certain newand useful Improvements in Gilsonitic Products and Their Manufacture,whereof the following is a specification.-

Our invention relates to gilsonitic products and their manufacture, andmore espe cially to products and materials obtainable from gilsonitethrough sulphona-tiontreatment and to processes and methods connectedwith such treatment. lVehave found that, by treatment of this character,there can be derived from, gilsonite andgilsonitic substances variousnew and useful products ofunique properties, and we-havedevised variousnovel processes, steps, and methods for accomplishing this to the bestadvantage. Certain of our processes and methods can .also be adapted andextended to hydocarbon substances or materials other than gilsoniticones,-especially those of mineral origin. The various phases of ourinvention will be specifically described hereinafter in accordance withthe best mode of applying them ina practical way at present known to us,while the real scope and essence of the inventionwill be indicated inour claims.

As a gilsonitic material to be treated, we ordinarily prefer gilsonitedistillate to native gilsonite itself. Wehave obtaineda much greateryield of sulphonic products from the treatment by preparing thedistillate some time in advance and allowedato age for a considerableperiod before being treated. Such distillate may be prepared as followsI Gilsonite as received from: the time is charged into an iron or steelstill, fired with gas or oil (or otherwise suitably' heated), andconnected to a suitable condenser,- such as an iron pipe condenserwater-cooled.

' 7 Any convenient quantity of gilsonite may be chargech say 600 poundsto several tons.

"vapors under the single .ture approaches some 550 Application filedAugust 28, .1919. Serial No. 320,5}4.

The still being closed and. heat applied gradually, the gilsonite willliquefy and collect in the bottom of the still, and vapor and gasevolving from it will fill the top of the stlll and pass over into thecondenser. As the heating progresses, temperature readings should betaken from time to time on the body of vapor in the upper portion of thestill, as well as on the body of liquid beneath may be special octhem,we here andit; (Excepting as there casion for distinguishing hereinaftercomprehen'd mingled gases and term vapor, for the sake of brevity; Forconvenience, we refer tovarious stages of operations by thecorresponding vapor temperatures, unless otherwise specially noted.) Theeffect of the progressive heating of. the gilsonite is to graduallybreak it up and decompose it chemically,whence, mainly, the evolution ofvapor. .The coming off of vapor from the still begins at a temperatureof some 165 F., and continues up to or even beyond cokmg temperatures.

Up to the point where-the vapor tempera- F., the distillation may becarried out as rapidly as the contents of the still can bemade to absorbheat. At this point, however, some exothermic or other peculiar actionoccurs, so that the evolution of vapor in thestill tends 'to becomeexcessively rapid. Unless, therefore, the previous heating has beenlaspecially slow, it is necessary to reduce the application of heatingvery greatly as this critical point is approached, in order thatundistilled iquid may not be carried over into the condenser,and clog itup so as to render it unusuable. In practice, it will usually be foundconvenient to cut down the fire some 100" Earn advance of thistemperature.

Once this critical point is well passed, the

fire'may be increased. and the distillation pushed on as rapidly asdesired to its conclusion. In practice, the heating need not be carriedfurther than a temperature of some850 F., measured on the solid cokeproduct collecting in thebottom of the still.

. WYhile the vapor coming off from the still may all be led into theiron pipe condenser,

P, HAYDEN, OF RARITAN TOWN- IBARBER ASPHALT COMPANY; OF

as above suggested,.and all'of the strictly v length andproviding-itwith a trap. With this arrangement, the heavier portion ofthe normally liquid products will be condensed bythe cooling effect ofthe atmosphere uponthe pipe (which thus acts as a sort of auxiliarycondenser), and will collect in the trap,

. whence it can be drawn off from time to F.,t0 600 F.,subsequently timeand added to the liquid products drawn from the condenser itself. Thetrap also affords ameasure of, protection againstthe effects of toorapid heating at thecritical temperature above mentioned.

'The crude distillate thus obtained contains some 2 to 5% water, whichmay be eliminated by settling it out in a settling tank.

We prefer not to treat the Water-freed primary, crude distillate thusproduced directly, in ross, but to separate it into a plurality ofdifferent portions by fractionation'or reduction. The following examples(wherein the temperatures given are the vapor temperatures in the still,unless otherwise .stated) will sufiiciently illustrate themost-convenient met ods of redistillation:

(1) Condense separately the vapors coming from the still .up to 475 F.and from 4.7 5 drawing off as residuum the oil unvaporized at the lattertemperature, or allowing it to remain and mix with the next charge ofcrude oil.

(2) Condense separately the vapors up to 475 n; from 475 F. to 650 F.;and

from 650 F. until the temperature of the material in the bottom of thestill is about 850 F. By this procedure, an amount 0 coke equal to.about 2% of the crude oil charge will be produced.

In either of these cases, considerable destructive action, occurs in theproductionof the higher fractions,especially the last.

(3) Three fractions nearly similar to those described under (2) may beobtained at temperatures some 100 F. lower than those mentioned bycarrying out the redistillation as described in U. S. Patent 87 7 ,620,granted Jan. 28, 1908, to Wells, blowing carbon dioxide or other inertpermanent gas through the liquid in the still. In this case, thedestructive action is much less. It is advantageous to pass. the gas andvapor com-- ing off through a filter of fullers earth in the dome of thestill, on its way to the condenser. A residuum of heavy oil willpreferably be left in the still, as described under (1).

The gas tains ammonia, which can be segregated as ammonium sulphate by asulphuric scrubbing operation. The coke from both distillations also hasa nitrogenous content recoverable by a similar operation in connectionWith conversion thereof into fuel .gas

by incomplete combustion in a by-product gas-producer. the crudedistillate also in solution, which may, if desired be also convertedinto ammonium sulphate. For these operations for recovery of ammonia maybe used the unconsumed portion of the sulphuric reagent employed in thepurification and sulphonation treatments hereinafter described.

Of the distillates contains ammonia thus produced, we gen.-

erally prefer to treat the intermediate one.

drior to sulphonation treatment, however, we prefer to sub cct thegilsomtic material to preliminary purifying treatment with a sulphuricreagent, thus removing therefrom organic bases, olefines, and otherimpurities that might alter or impairthe character and utility of thefinal products. This preliminary sulphuric' treatment may be carried outby agitation of the gilsonitic material with about 5% of sulphuric acidof oil of vitriol grade-d. e., about 66 Be.-for about onehalf hour. Itis desirable to repeat the operation (using fresh acid) one or moretimes.

After this preliminary step,

sulphonation treatment may be carried out by subfrom the primarydistillation con- I The water eliminated from' jecting the purifiedgilsonitic oil to the action of a sulphonating reagent, under the usualsulphonating conditions. The sulphonating reagents which we prefer touse are oil of vitriol, such as mentioned above, and fuming sulphuricacid Or oleum. It is desirableto conduct this treatment in a cast ironvessel, using mechanical agitation rather than air agitation in order toavoid f such contamination with atmospheric moisture as might interfereWith the desired reaction. v

We have found that the quality of the final products is improved bycarrying out this treatment progressively, with successive portions ofreagent, and segregating the reaction products, as formed, from thematerial being treated, so that each of the successively acting portionsof reagent shall be perfectly fresh and-untainted with such reactionproducts. Further improvement can be obtained .by starting withrelatively weak reagent, and using more and more reactive or energeticreagent as the treatment progresses. This may be done in a succession,of separate operations upon a single lot of material with differentportio s of reagent, rather than in one single operationsay four suchwith an amount of reagent equal to 20% ofthe material treated. Thus forthe first treatment, the reagent may be oilof vitriol alone; for the"second, a mixture of 15 parts oil of vitriol and 5 parts oleum; for thethird, a mixture of oil of vitriol and oleum in equalparts; for thefourth, a mixture of 5 parts oil of vitriol and 15 parts oleum. Each ofthese treatments may last about twohours.

If, on the other hand, it is desired to carry out sulphonation treatmentall at once, in a single operation, rather than progressively; it may bedone by mechanical agitation for some eight hours,.-.using, say, anamount of sulphonatin'g reagent equal to 80% of-the material treated andconsisting of 50 parts oil of vitriol and 30 parts oleum.

At the end of each treatment or operation,-

the charge in the agitator is allowed to stand an hour or more, when itwill be found to have. separated into two distinct layers; a top layerof residual or mother. oil, and a bottom layer of acid sludge. Thislatter should be drawn off an thus segregated prior to the next tretment of the mother material.

The residual oil remaining after. the last treatment may beneutralized,.as with sodium hydrate solution (preferably of spe- I cificgravity greater than 30 B.,'in order to avoid emulsification). After theexcess of caustic has been drawn oil, the resultant alkaline oil shouldpreferably not be washed, on account of its emulsifying tendency; but itmay instead be distilled" with steam, in order to improve its color, andfiltered through fullers earth .for the same purpose. This gilsoniticsulphonation residual oil as thus purified is a thin, clear oil;substantially colorless, odorless, and tasteless; and suitable for aboutthe same uses as hi hlv refined petroleum. If desired, the distllla--tion above mentioned may be carried out fractional'ly, so as to yielddifferent oils more specially suitable for particular pur- .oses.

r It is' preferable that the lots of sludge obtained from differentsulphonation treatments be further treated or worked up individually,since the various treatments.

yield final products having somewhat different properties. Thissulphonation sludge contains, as principal components, unconsumedsulphonating reagent, Water-soluble organic sulphonic products, and oilproduced from the mother oil by chemical action incident to thesulphonationtreatment. It also contains, as impurity, an inconsider ableamount of the mother oil itself (which may, if subsequently segregated,be neutreatments, each described, The top layer tralized along with thatobtained :as above I described), and some small amount of other organicproducts. The proportions .of the the rest of the sludge-can be effectedby addition thereto of asolvent of the sulphonating reagent; :for thispurpose, the sludge may be diluted with an equal Weight of water.Preferably the Water is laced in a lead-lined, Water-jacketed vessel:and the sludge gradually introduced at such a rate that the temperatureshall not rise excessively,110 F. being a perfectly safe limit. Theoperation is declcledly exot ermic, and

sulphur dioxide is copiously evolved. The

dilute sludge is allowed to stand some eight "to twelve hours,moreorless,-at a temperature of 150 F., or thereabout; During this period,separation into three distinct layers takes place, successively drawnoffand thus segregated. The bottom layer is a dilute aqueous solution-ofthe excess of sulphonating reagent, discolored by some slight amount oforand these may be;

gan-ic impurity; the middle layer comprises the water-soluble organicsulphonic mate rial, contaminated with an inconsiderable amount of thesolutionthat forms the bottom layer and with a small portion of theingredlents of the top layer; and thetop layer contains the reaction oilcomponent andthe residual mother-oil impurity, etc., mentioned above.(In some cases, as indicated above, the top layer may be entirelyabsent. Y

Comlng, now, to the further disposition or treatment of these separationproducts, the, dilute acid of the bottom layer may be used for therecovery of ammonia as above (when present) may be neutralized withsodium hydrate and washed with water until free from alkali. Theresulting gilsonitic sulphonation sludge oil isa viscous liquid;of-slow-drying or semi-drying character; and usually'of dark,reddish-brown color and slight, inoffensive odor, Vaseline.

somewhat'suggesting that of It is soluble in benzole or naphtha andinsoluble in. alcohol, when freshly I I also seems to render the fullydried linseed tougher and more elastic.

The water-soluble organic sulphonic material .of the middle layer givesan acid reaction, and has, in general, the useful properties ofsulphonic acids. In appropri-. ate combinations, therefore,- itscharacter istic radical or radicals constitute a useful agent for manydifferent 1.)urposes-acting as hydrolyzer or saponifier for oils, "ate,and other glycerides or fatty substances, when employed in the usualmanner, and having excellent detergent and emulsifying properties. Forthe first of these uses, at least, this sulphonie agent is serviceablein the impure acid form in which it exists in the middle layer, althoughits color characteristics and the efficiency of its hydrolyzing actionare not so good as after purification. To purify it of the organic toplayer material (the principal contaminating impurity), it may beneutralized, which has the effect of setting free this top layermaterial and allowing it to float to the surface and be readily removed.For hy'drelyzing purposes, the purified saltthus obtained may bereconverted (by means of sulphuric orother. acid) to yield the agent inpurified free acid form; while for detergent or emulsifyingpurposes, thepurified salt. form of the agent will ordi narily be preferred to theacid form. The 'sulphonic material of the middle layer can also be freedfrom organic contamination without neutralization, by merely dilutingthe middle layer with water freely,-whichwill allow the organic materialto come to the surface as described above.

If desired, the salt form of the'reagent may be obtainedvfree from bothorganic material and sulphates- For this purpose, the middle layer maybe diluted with water and barium sulphate precipitated therefrom (somelittle barium salt of the reagent being unavoidably thrown down also) byaddition of barium carbonate in just sufficient amount to fully satisfythe sulphuric acid; this leaves the free acid reagent in solution. Y After filtration, the organic material can be set free for. removal fromthe solution as before. v

In both purified and unpurilied states, the

sulphonic products from the later sulphonation treatments have greaterhydrolyzing power than those from' the earlier treatments.

It is most convenient and desirable to handle, pack, and ship an agentof this sort in the'form of a dry, solid, stable salt, rather than inits more active free acid form,- which is, besides, in the presentinstance, more'diificult to dry. It is, of course, preferable that theparticular salt that is to be so used commercially be produced at theoutset, in the freeing of the agent from organic contamination asdescribed in the precedphonic substances ing paragraphs. For detergentand emulsifying purposes, narily be preferable, on account of itsrelatively low cost. For saponifying or hydro: lyzing purposes, however,it is peculiarly advantageous to employ as the commercial material asalt with a volatile base, and to produce the active, free acidsaponitier there from by acidulation when it is to be used,

either before or in the actual treatment of the glycerides,-on accountof the facility thus ailorded for securing glycerine water free fromsa-ponifier, acidulant, or other deleterious impurity. For this purpose,the ammonium salt form of the agent is especially suitable lVhen this isused, the glycerine water subsequently obtained will contain only acidsaponiiier, acidulant, (usually sulphuric acid), and ammonium salt ofthe acidulant. By addition to this glycerine waterof a suitable base orsalt (such as calcium hydrate or barium carbonate), insoluble salts ofthe acidulant and the saponifier vill be formed and precipitated. Thiswill leave in solution in the glycerine water, as an impurity only anunstable combination (annnoui um hydroxide or carbonate) whosecomponents can be volatilized and driven off by boi ing.

As to the general properties of these gilsenitic derivative sulphonicmaterials, it is to be observed that the alkali salts (i. e., bothainoniu n and alkali metal salts) are watersoluble, aswell as the acid;whi e the alkaline earth and the other metal salts general- 1y arewateninsoluble. (These properties, itwill be seen, specially adapt thesematerials'to the modes of use described in the preceding paragraph). Asit exists in the middle layer, the acid, material is a thick, viscousfluid, dark or black, with a brown un-.

dertone in a thin film. Aside from the organic top' layer contamination,it is soluble in alcohol. The alkali salts are also soluble inaIcohol,'-which fact affords another convenient method of freeing themfrom sulhate contamination.

the sodium salt will ordi-' We have hereinbefore spoken of sulphonatingreagents, sulphonation treatment, and sulphonation reaction or sulphonicproducts, etc, using these expressions in reference to the chemicalcharacter and mode of. use of the reagent employed in the principaltreatment describedabove, or to the useful roperties of productsresulting therefrom. lVe do not. however, mean by this language hat oursulphonic products are true 5111 in thevsense oflhaving sulphonicradicals, -since we are without clear evidence on .this point.

Returning,- now, to the residualoil remaining from the last sulphonation, we desire to call attention-:to a mode of dealing with italternative to that above set forth. In this method,'the first step isto :wash

the excess of alkali. If desired, it may also.

be distilled, as'above; This mode of treatment; f greatly improves thecolor of the 'purifie d residual oil finally obtained.

/The organic material dissolved or. extracted from the residual oil bythe, alcohol appears to be the cause of the emulsifying i property ofthe oil; for when recovered (by 'sulp purity.

distillation of the alcohol), it itself presents this same property. Asthus obtained, this extract derivative is' an acid substance, brown toblack. in color, and with slight odor. Appropriate combinations of itscharacteristic radical or radicals present useful roperties similar tothose of our other lionic agent described abov'e,'-though' somewhatsuperior in degree,-and are serviceable for the same purposes and in thesame way. -We have no proof, however, that it is a true sulphonicsubstance or sulphonation product, or that its characteristic radical issulphonic. In both acid and salt forms, this gilsonitic sulphonic agentis similar to the other as regards water-solubilities; but with respectto organic solvents, it issharply distinguished. Thus both the acid andsalt forms are soluble in most organic solvents,-such as benzole,alcohol, petroleum naphtha, or other distillates,' and both salt andacid forms are more freely soluble in such solvents than in water. Thedissolution ofthe' acid material in water is peculiar (probably owin toimpurity),

in that aswater is gradua added 'toythej' .material,-it'firstgelatinizes and then goesv more freely into solution. Therelativehydrolyzin'g, detergent, and emulsifyingproperties of'these gilsoniticderivative sulphonic materials (i. e., acid and salts) are similar tothose of the others.

Having thus described our invention, we claim 1. The process whichconsists in purifying gilsonltic material by sulphuric treatment;subjecting the purified product to the action of .a sulphonating reagentunder sulphonating conditions and segregating the resultant sludge; seegating the sulphonic products in the slu ge from the remainder thereof;and freeing the segregated sul--- phonic products from contaminating im-2. The process which consists in purifying gilsomticmaterial bysulphuric treatment; subjecting the purified product to the action of asulphonating reagent under sulphonating conditions and segregating the,

resultant sludge; dissolving the unconsumed reagent in the sludge with asolvent, and thus causing reaction products in the sludge a theunconsumed sulphonatin to separate from one another andfrom the.

solution of reagent by gravity.

in the sludge from one another and from reagent by addition to thesludge of a so vent of such reagent.

4. The process which consists in treating gilsonitic material with asulphonating reagent under sulphonating conditions, dissolving productsof the reaction in an excess of such reagent; segregating the resultantsludge solution from the mother material; removing .the' excess ofsulphonating re agent from said sludge solution by solution of suchexcess of sulphonating reagent with another solvent; and separating saidreac fl" tion products from one another and from the solution ofsolvents by gravity.

5. The process of preparing sulphonation reaction products fromgilsonitic material which comprises subjectin the gilsonitic material tosulphuric puri cation, thereby removing organic bases, olefines, orother impurities; and subjecting the thus purified material to theaction of a sulphonating reagent under sulphonating conditions.

6. The process of preparing sulphonation reaction products fromgilsonitic material which comprises purifying the gilsonitic materialwith oil of -vitriol grade sulphuric acid and subjecting the thuspurified material to the action of a sulphonating reagent undersulphonating conditions.

7 7 The step in the manufacture of sulphonation reaction products from'hydrocarbon material which consists in subjecting said material tosuccessive sulphonation treatments with different portions ofsulphonating reagent, segregatingthe sludge of each treatment. from themother material prior to the next treatment of said material.

8. The step. in the manufacture of sul- 9. The method which consists insubject- 1 inggilsonitic distillate oilto progressive sulphonationtreatment with successive portions of fresh sulphonating reagent, eachunta-inted with reaction products of such treatment.

10. The method which consists in subjecting gilsonitic material toprogressive sulphonation treatment with fresh sulphonating reagent ofgreater and greater reactivity,

( segregating the reaction products, as formed,

' from the material being treated.

11. The method of manufacturing hydrocarbon sulphonation sludge productswhich consists 1n producing separate lots of-such sludge by a pluralityof successive sulphonation treatments of a single lotof hydrocarbonmaterial with different portions of sulphonating reagent, and furthertreating such lots of sludge individually.

12. The method ing up a plurality of lots of such sludge from a singlelot'of gllsomtic material.

13. The method oi trcatmg g1ls0n1t1c sulphonation sludge which consistsin segre-j ing the uneonsumed sulphonating reagent therein with asolvent, and separating the sulphonic and other reaction products in thesludge from one another and from the solution of reagent by gravity.

15. A gilsonitic snlphonic material; serviceable as an agent for thehydrolysis of glycerides; detergent: and characterized by a radicalwhose alkali= salts and free acid arew'atensoluble, but whose alkalineearth salts are water-insoluble.

16. A sulphonation product derived from gilsonite distillate; havinggenerally the useful properties of true sulphonic substances; andcharacterized by a radical whose alkali salts and free acid are waterofmanufacturing gilsomtlc sulphonation sludge products winch .consists 1nseparately preparing and Worksoluble, but. whose alkaline earth andother metallic salts generally are water-insoluble.

17. A sulphonic material derived from gilsonitie sulphonation sludge asa watersoluble separation product; characterized by a radical whosealkali "salts and free acid are water-soluble, but whose alkaline earthsalts are water-insoluble.

18. A sulpili'onie derivative of sulphurically purified gilsoniticmaterial; having in general, the useful properties of true sulphonicsubstances.

19. A sulphonic derivative of the residual from antecedent sulpho-nationtreatment of gilsonitic material;

stances; and characterized by superior hydrolyzing power as compared'with the corresponding product from such antecedent snlphonationtreatment.

20. A sulphonie derivative of the residual "from antecedent sulphonationtreatment of sulphurically purified gilsonite distillate.

21. A gilsonitic sulphonic material serviceable as an agent for thehydrolysis of glycerides; comprising a salt of a volatile base whichyields, when acidulated, an active water-soluble saponifier.

22. A gilsonitic sulphonic material serviceable as an agent for. thehydrolysis of glycerides; comprising a water-soluble ammonium salt whichyields, when acidulatcd an active water-soluble saponifier.

In testimony whereof,.we have hereunto signed our names at M'aurer, N. Jthis 25th day of August, 1919.

CHARLES N. FORREST. "HAROLD P. HAYDEN. ORIN R. DOUTHETT.

having, in general, the 'useful properties of true sulphonlc sub-

